EP0023912B1 - Heat curable compositions - Google Patents

Heat curable compositions Download PDF

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Publication number
EP0023912B1
EP0023912B1 EP80900361A EP80900361A EP0023912B1 EP 0023912 B1 EP0023912 B1 EP 0023912B1 EP 80900361 A EP80900361 A EP 80900361A EP 80900361 A EP80900361 A EP 80900361A EP 0023912 B1 EP0023912 B1 EP 0023912B1
Authority
EP
European Patent Office
Prior art keywords
heat curable
accordance
cationically polymerizable
curable composition
organic material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP80900361A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0023912A1 (en
EP0023912A4 (en
Inventor
James Vincent Crivello
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by General Electric Co filed Critical General Electric Co
Publication of EP0023912A1 publication Critical patent/EP0023912A1/en
Publication of EP0023912A4 publication Critical patent/EP0023912A4/en
Application granted granted Critical
Publication of EP0023912B1 publication Critical patent/EP0023912B1/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
    • C08G65/10—Saturated oxiranes characterised by the catalysts used
    • C08G65/105—Onium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00—General processes for preparing compounds provided for in this subclass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to heat curable compositions comprising a cationically polymerizable organic material, for example, an epoxy resin, a hydroxyarylsulfonium salt and an organic oxidant.
  • a cationically polymerizable organic material for example, an epoxy resin, a hydroxyarylsulfonium salt and an organic oxidant.
  • Organic resins for example epoxy resins can be thermally cured by using an effective amount of an aromatic onium salt such as an aryl iodonium salt and a reducing agent, for example, a thiophenol.
  • Resins can be cured using triphenylsulfonium salts, for example, see US ⁇ A ⁇ 3412046, and substituted trialkyl sulfonium salts or dialkyl aryl sulfonium salts, see US-A-4058400.
  • the present invention is based on the discovery that such organic resin also can be thermally cured with an organic oxidant, such as an organic peroxide in combination with an effective amount of certain hydroxyaryl sulfonium salts, for example, dimethyl-4-hydroxy-3,5-dimethylphenyl sulfonium hexafluoroarsenate, as well as peroxides, azo-bis-alkyl nitriles, p-chloranil, or 3,3',5,5'tetramethyl 4,4'-diphenoquinone.
  • an organic oxidant such as an organic peroxide in combination with an effective amount of certain hydroxyaryl sulfonium salts, for example, dimethyl-4-hydroxy-3,5-dimethylphenyl sulfonium hexafluoroarsenate, as well as peroxides, azo-bis-alkyl nitriles, p-chloranil, or 3,3',5,5'tetra
  • heat curable compositions comprising (A) a cationically polymerizable organic material, (B) an effective amount of a thermal curing agent capable of effecting the cure of the cationically polymerizable organic material including an organic oxidant selected from organic peroxides, azo-bis-alkyl-nitriles, p-chloranil and 3,3',5,5'-tetramethyl-4,4'-diphenoquinone wherein the thermal curing agent also includes a sulfonium salt having the formula
  • R' monovalent radicals include CH 3 -, ⁇ C 4 H 9 ⁇ , C 2 H 5 ⁇ , CH 3 0-, (CH 3 ) 3 C ⁇ , C 6 H S CH 2 -
  • R' alkylene radicals include ⁇ (CH 2 ) 4 ⁇ , ⁇ (CH 2 ) 5 ⁇ , ⁇ CH 2 ⁇ CH 2 ⁇ O ⁇ CH 2 ⁇ CH 2 ⁇ , and ⁇ CH 2 ⁇ CH 2 ⁇ S ⁇ CH 2 ⁇ CH 2 ⁇ .
  • Hydroxyphenyl sulfonium salts included are,
  • Organic oxidants which can be used in the practice of the invention in combination with the hydroxy arylsulfonium salts of formulas 1 and 2 to effect the cure of the cationically polymerizable organic material are, for example, organic peroxides such as ketone peroxides, peroxy acids, dibasic acid peroxides, aldehyde peroxides, alkyl peroxides, hydroperoxides, alkyl peroxyesters, diperoxide derivatives, for example, t-butyl peroxypivalate, 2,4-dichlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, decanoyl peroxide, propionyl peroxide, acetyl peroxide, t-butyl peroxyisobutyrate, p-chlorobenzoyl peroxide, benzoyl peroxide, hydroxyheptyl peroxide, cyclohexanone peroxide, 2,
  • organic oxidants which also can be used in the practice of the invention include azo-bis alkyl nitriles and other azo compounds, such as quinones, such as iodoso aromatic compounds, such as iodosobenzene, 4-nitroiodosobenzene, iodosobenzene diacetate, 4-chloroiodosobenzene, 4-methoxyiodosobenzene, 4-iodosobiphenyl or 2-chloroiodosobenzene diacetate.
  • quinones such as iodoso aromatic compounds, such as iodosobenzene, 4-nitroiodosobenzene, iodosobenzene diacetate, 4-chloroiodosobenzene, 4-methoxyiodosobenzene, 4-iodosobiphenyl or 2-chloroiodosobenzen
  • Cationically polymerizable organic materials which can be used to make the heat curable compositions of the present invention include epoxy resins, thermosetting organic condensation resins of formaldehyde, vinyl organic prepolymers or cyclic ethers.
  • epoxy resin as utilized in the description of the cationically polymerizable compositions of the present invention, includes any monomeric, dimeric or oligomeric or polymeric epoxy material containing one or a plurality of epoxy functional groups.
  • those resins which result from the reaction of bisphenol-A (4,4'-isopropylidenediphenol) and epichlorohydrin, or by the reaction of low molecular weight phenol formaldehyde resin (Novolak resin) with epichlorohydrin can be used alone or in combination with an epoxy containing compound as a reactive diluent.
  • Such diluents as phenyl glycidyl ether, 4-vinylcyclohexene dioxide, limonene dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide or allyl glycidyl ether may be added as viscosity modifying agents.
  • the range of these compounds can be extended to include polymeric materials containing terminal or pendant epoxy groups.
  • examples of these compounds are vinyl copolymers containing glycidyl acrylate or methacrylate as one of the comonomers.
  • Other classes of epoxy containing polymers amenable to cure using the above catalysts are epoxy-siloxane resins, epoxy-polyurethanes and epoxy-polyesters. Such polymers usually have epoxy functional groups at the ends of their chains. Epoxy-siloxane resins and method for making are more particularly shown by E. P. Plueddemann and G. Fanger, J. Am. Chem. Soc. 80 2632-5 (1959).
  • epoxy resins can also be modified in a number of standard ways such as reaction with amines, carboxylic acids, thiols, phenols or alcohols as shown in U.S. patents 2,935,488; 3,235,620; 3,369,055, 3,379,653; 3,398,211, 3,403,199; 3,563,840; 3,567,797; 3,677,995.
  • Further coreactants which can be used with epoxy resins are hydroxy terminated flexibilizers such as hydroxyl terminated polyethers, hydroxy terminated polyesters, etc., shown in the Encyclopedia of Polymer Science and Technology, Vol. 6, 1967, Interscience Publishers, New York, pp. 209-271 and particularly p. 238.
  • thermosetting organic condensation resins of formaldehyde which can be used in the practice of the present invention are, for example, urea type resins, such as or phenol-formaldehyde type resin, such as where x and n are integers having a value of 1 or greater; or alkoxy silanes having the formula, where R is a C (1-7) alkyl radical, R S is selected from R 7 radicals and C( 6 - 13 ) aryl radicals and halogenated derivatives, m is an integer equal to 1 to 4, n is an integer equal to 0 to 3 inclusive and m + n is equal to 4.
  • urea type resins such as or phenol-formaldehyde type resin, such as where x and n are integers having a value of 1 or greater
  • alkoxy silanes having the formula, where R is a C (1-7) alkyl radical, R S is selected from R 7 radicals and C( 6 - 13 ) aryl radicals and halogenated
  • melamine thiourea resins melamine, or urea aldehyde resins, cresolformaldehyde resins and combinations with other carboxy, hydroxyl, amino and mercapto containing resins, such as polyesters, alkyds and polysulfides.
  • a further category of the organic materials which can be used to make the polymerizable compositions are cyclic ethers which are convertible to thermoplastics. Included by such cyclic ethers are, for example, oxetanes such as 3,3-bis-chloromethyloxetane, alkoxyoxetanes as shown by U.S. Patent 3,673,216, assigned to the same assignee as the present invention; oxolanes such as tetrahydrofuran, oxepanes, oxygen containing spiro compounds, trioxane, dioxolane, etc.
  • oxetanes such as 3,3-bis-chloromethyloxetane, alkoxyoxetanes as shown by U.S. Patent 3,673,216, assigned to the same assignee as the present invention
  • oxolanes such as tetrahydrofuran, oxepanes, oxygen containing spiro compounds, triox
  • cyclic esters such as (3-Jactones, for example propiolactone, cyclic amines, such as 1,3,3-trimethyl-azetidine and organosilicone cyclics, for example, materials included by the formula, where R" can be the same or different monovalent organic radical such as methyl or phenyl and p is an integer equal to 3 to 8 inclusive.
  • organosilicon cyclic is hexamethyl trisioloxane, octamethyl tetrasiloxane, etc.
  • the products made in accordance with the present invention are high molecular weight oils and gums.
  • the heat curable compositions of the present invention can be made by blending the cationically polymerizable organic material with an effective amount of the thermal curing agent.
  • an effective amount of the thermal curing agent there can be used 0.1 to 10 percent by weight of a hydroxyarylsulfonium salt based on the weight of cationically polymerizable organic material.
  • a hydroxyarylsulfonium salt based on the weight of cationically polymerizable organic material.
  • the resulting curable composition can be in the form of a varnish having a viscosity of from 0.001 to 100 kg/m.s at 25°C or a free flowing powder, depending upon the nature of the cationically polymerizable organic material.
  • the curable compositions can be applied to a variety of substrates by conventional means and cured to the tack-free state within 0.5 to 20 minutes, depending upon the temperature employed.
  • an organic solvent such as nitromethane, acetonitrile
  • a curable compositions may contain inactive ingredients, such as silica, talc, clay, glass fibers, extenders, hydrated alumina, carbon fiber process aids, etc., in amounts of up to 500 parts of filler per 100 parts of cationically polymerizable organic material.
  • the curable compositions can be applied to such substrates as metal, rubber, plastic, molded parts or films, paper, wood, glass, cloth, concrete, ceramic, etc.
  • curable compositions of the present invention are, for example, protective, decorative and insulating coatings, potting compounds, printing inks, sealants, adhesives, molding compounds, wire insulation, textile coatings, laminates, impregnated tapes or varnishes.
  • Example 1 The procedure of Example 1 was repeated, except that Celanese SU8 (Trade Mark), epoxy novolak resin was substituted for the diglycidyl ether bisphenol-A epoxy resin.
  • the resulting heat curable composition required eight minutes to harden at 120°C.
  • Methylon @ resin a phenolformaldehyde resole of the General Electric Company
  • 3 parts of t-butyl hydroperoxide were then heated at 150°C.
  • the mixture having the t-butyl hydroperoxide cured to a hard crosslinked insoluble resin.
  • the mixture free of the organic oxidant remained substantially unchanged.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP80900361A 1979-02-12 1980-08-25 Heat curable compositions Expired EP0023912B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/011,102 US4230814A (en) 1979-02-12 1979-02-12 Heat curable compositions
US11102 1979-02-12

Publications (3)

Publication Number Publication Date
EP0023912A1 EP0023912A1 (en) 1981-02-18
EP0023912A4 EP0023912A4 (en) 1982-02-05
EP0023912B1 true EP0023912B1 (en) 1985-07-31

Family

ID=21748899

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80900361A Expired EP0023912B1 (en) 1979-02-12 1980-08-25 Heat curable compositions

Country Status (5)

Country Link
US (1) US4230814A (enExample)
EP (1) EP0023912B1 (enExample)
JP (1) JPS56500496A (enExample)
DE (1) DE3070910D1 (enExample)
WO (1) WO1980001723A1 (enExample)

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US4336363A (en) * 1979-02-12 1982-06-22 General Electric Company Heat curable compositions containing sulfonium salts
US4299938A (en) * 1979-06-19 1981-11-10 Ciba-Geigy Corporation Photopolymerizable and thermally polymerizable compositions
US4339567A (en) * 1980-03-07 1982-07-13 Ciba-Geigy Corporation Photopolymerization by means of sulphoxonium salts
US4367251A (en) * 1980-04-21 1983-01-04 General Electric Company UV Curable compositions and substrates treated therewith
US4319974A (en) * 1980-04-21 1982-03-16 General Electric Company UV Curable compositions and substrates treated therewith
US4383025A (en) * 1980-07-10 1983-05-10 Ciba-Geigy Corporation Photopolymerization by means of sulfoxonium salts
US4374751A (en) * 1980-08-08 1983-02-22 General Electric Company Polymerization initiator compositions
US4398014A (en) * 1980-11-04 1983-08-09 Ciba-Geigy Corporation Sulfoxonium salts and their use as polymerization catalysts
US4388450A (en) * 1981-03-13 1983-06-14 General Electric Company Aromatic polyvinyl ethers and heat curable molding compositions obtained therefrom
US4387216A (en) * 1981-05-06 1983-06-07 Ciba-Geigy Corporation Heat-polymerizable compositions comprising epoxide resins, aromatic sulfoxonium salts, and organic oxidants
US4442197A (en) * 1982-01-11 1984-04-10 General Electric Company Photocurable compositions
US4554342A (en) * 1984-07-30 1985-11-19 Shell Oil Company Heat-curable compositions comprising an epoxy resin, an amine and a sulfonium salt
US4708925A (en) * 1984-12-11 1987-11-24 Minnesota Mining And Manufacturing Company Photosolubilizable compositions containing novolac phenolic resin
US4579931A (en) * 1985-01-28 1986-04-01 Shell Oil Company Heat-curable composition
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US4581436A (en) * 1984-12-24 1986-04-08 Shell Oil Company Heat-curable composition
US4544732A (en) * 1984-12-24 1985-10-01 Shell Oil Company Heat-curable composition
US4611040A (en) * 1985-06-05 1986-09-09 Ppg Industries, Inc. Fluoride ion as a curing catalyst for silicon-containing resins
MY106951A (en) * 1987-12-08 1995-08-30 Mitsui Chemicals Inc Active energy ray-curable composition and optical recording medium having cured product of the composition
US5399596A (en) * 1988-03-03 1995-03-21 Sanshin Kagaku Kogyo Co., Ltd. Polyfluoride sulfonium compounds and polymerization initiator thereof
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US5667934A (en) * 1990-10-09 1997-09-16 International Business Machines Corporation Thermally stable photoimaging composition
JPH055006A (ja) * 1990-11-16 1993-01-14 Nippon Kayaku Co Ltd カチオン重合性有機材料組成物および当該組成物の安定化法
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US6066889A (en) 1998-09-22 2000-05-23 International Business Machines Corporation Methods of selectively filling apertures
US6204456B1 (en) 1998-09-24 2001-03-20 International Business Machines Corporation Filling open through holes in a multilayer board
US6498200B1 (en) * 1999-01-12 2002-12-24 Namics Corporation Cationically polymerizable resin composition
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US8324319B2 (en) * 2007-11-20 2012-12-04 Sridhar Laxmisha M Redox-induced cationically polymerizable compositions with low cure temperature
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Also Published As

Publication number Publication date
JPS56500496A (enExample) 1981-04-16
EP0023912A1 (en) 1981-02-18
DE3070910D1 (en) 1985-09-05
US4230814A (en) 1980-10-28
WO1980001723A1 (en) 1980-08-21
EP0023912A4 (en) 1982-02-05

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